Palladium-catalyzed intermolecular asymmetric hydroamination with 4,4′-disubstituted BINAP and SEGPHOS

A family of tunable precatalysts [Pd((S)-L*)(NCMe)(2)](OTf)(2), where L* is 4,4'-disubstituted BINAP or SEGPHOS, was synthesized and used for the asymmetric intermolecular hydroamination of aniline to vinylarenes with ee values of up to 85 %, and it is believed that the bulky groups on the 4,4'-positions and the narrower dihedral angle of the biaryl moiety are responsible for the ee enhancement in these reactions.